Process and apparatus for treating oils



Aug. 27, 1929. G. D. WHITE PROCESS AND APPARATUS FOR TREATING OILS Filed March 15, 1920 5 Sheets-Sheet 1 Aug. 27, 1929. G. D. WHITE 1,726,230

PROCESS AND APPARATUS FOR TREATING OILS Filed March 15. 1920 5 Sheets-Sheet 2 I ITlYI ln n F1 ['1 Aug. 27, 1929. e. D. WHITE 1,726,230 7 PROCESS AND APPARATUS FOR TREATING OILS Filedlarch 15. 1920 5 Sheets-Sheet 3 5% am-toz Aug. 27, 1929. G. D. WHITE PROCESS AND APPARATUS FOR TREATING OILS Filed larch 15. 1920 5 Sheets-Sheet 4 QMWNN Aug, 27, 1929. WHITE 1,726,280

PROCESS AND APPARATUS FOR TREATING OILS Filed March 15. 1920' s Sheets-Sheet 5 Patented Aug. 27, 1929 UNITED STATES PATENT OFFICE.

GEORGE 1'). WHITE, OF PORT ARTHUR, TEXAS, ASSIGNOR, BY MESNE ASSIGNMENTS, TO THE TEXAS COMFANY, OFNEW YORK, N. Y.,- A CORPORATION OF DELAWARE.

PROCESS AND APPARATUS FOR TREATING OILS.

Application filed March 15, 1920. Serial No. 365,955.

My invention relates to the treatment of hydrocarbon oils for the production of lower boilin products therefrom by heating or distilling the oil in the presence of aluminum chlorid or of compounds or mixtures thereof with hydrocarbons. 4

One object of my invention is to provide a relatively simple and effective process for continuously treating petroleum o1ls 1n which the aluminum chlorid is more effectively and completely utilized than has hitherto been considered possible.

Another object of my invention is to pro vide a process of continuously recovering aluminum chlorid from the sludge withdrawn from a still or cracking chamber in which it has been employed in connection with the treating or cracking of hydrocarbon oils.

Another object of my invention is to provide apparatus suitable for carrying out the aforesaid processes and particularly arranged and adapted for continuous operation.

Other objects and advantages of my invention will be set forth hereinafter and I will now describe my invention more in detail.

Referring to the drawings:

Figure 1 is a side elevation of a complete 30 apparatus constituting an embodiment of my invention and adapted for practicing my improved process.

Figure 2 is a front elevation of the apparatus shown in Figure 1.

Figure 3 is a partially diagrammatic elevation of the apparatus shownoin Figures 1 and 2, in which the various pipe connections are more particularly illustrated.

Figure 4.- is a partially sectional elevation 40 showmg the oil still or cracking chamber more in detail, the walls of the still being broken away to disclose the scraper or agitator within. I

Figure 5 is a sectional plan view taken 745 along the line 55 of Figure 4.

Figure 6 is a plan view of the still shown in Figure 4, particularly illustrating the driving mechanism for the scraper or stirrer which is located within the still. V

Figure 7 is a partially sectional elevation of a mixing chamber which forms a part of the apparatus shown in Figures 1 and 2 and in which aluminum chlorid is mixed with oil prior to its introduction into the still. The wall of the mixing chamber is broken away to disclose a stirrer which is mounted therein.

Figure 8 is a plan view of the mechanism shown in Figure 7 and Figure 9 is a sectional plan view taken along the line 9-9 of Figure 7.

Figure 10 is a partially sectional plan view of the furnace which forms a part of the apparatus and which supplies heat not only to the still, but also to a pair of coking or recovery stills located one on each side of the main oil treating still.

Figure 11 is a partially sectional elevation of the furnace and stills and Figure 12 is a side elevation at right angles to Figure 11. Figure 13 is a detailed view showing one of the jackets with which the aluminum chlorid recovery line is equipped.

Figure 14 is a sectional view taken on the line 1414 of Figure 13.

Figure 15 is a partially sectional detail of a scraper or cleaner for the joint in the aluminum chlorid recovery line.

Figure 16 is a diagrammatic view of an oil charging arrangement.

General description.

The apparatus comprises in general a furnace 20 having a main combustion chamber 21 for supplying heat to a main oil still 22 and auxiliary combustion chambers 23 and 2A for supplying heat to recovery stills 25 and 26; an aluminum chlorid-oil mixing chamber 27 an air condenser 28, a water condenser 29, and a collecting drum 30 from which the treated or cracked oil is withdrawn.

Fm'nace.

The main combustion chamber 21 of the furnace 20 has an arch 32 and a central pillar 33 which supports the bottom of the oil still at the front, it being supported at the back by the furnace wall 34 as clearly shown in Figure 10. In the preferred construction, as clearly indicated in Figures 10 and 11,

the bottom of the still 22 is protected from ed to support the coke stills and 26 as shown in Figures 11 and 12.

' The furnaces as illustrated are arranged for oil burners, but any suitable type of burner, or in fact, any suitable means for supplying heat to the stills may be employed.

arm ar still.

The main oil still 22 is vertically arranged and extends for a short distance above the brick work of the furnace in which it is supported. As shown in Figure 4, it is provided with discharge outlets 35 and 36 which may be opened to allow the sludge or residual products of the reaction including partially used aluminum chlorid to pass into the respective recovery stills 25 and 26. Connected to the still at the top is an oil vapor line 37 and a vertical pipe 38 which forms a gravity connection with-the mixing chamber 27. It is further provided with aluminum chlorid vapor line connections 39 and 40, which are provided with control valves 41 and 42 and lead into a common inlet pipe 43 which extends downwardly into the still below the oil level therein.

As shownyin Figures 3 and 15 the pipe 43 extends upwardly above the T connection 44 where it joins the lines 39 and 40, and is provided with a plum er. or scraper 45 which is arranged to keep t e pipe and the T connection. free from deposits. The scraper is attached to a scraper rod 46 which extends through a suitable stuifing box 47 at the upper end of the pipe 43 and is equipped. at its outer end with an operating handle 48.

A back trap line 49 leads into the still below the oil level as shown in Figure 3.

In order to prevent an accumulation of solid matter on the bottom of the still and to more thoroughly contact the oil with the aluminum chlorid T have provided a scraper or stirrer 50 composed of a vertical shaft 51 supported at the bottom of the still on a thrust bearing 52 and substantially at the centre of the still by a guide bearing 53.

Secured to the shaft and radiating therefrom are a plurality of scraper arms or paddles 54.

The shaft 51 extends upwardly beyond the top of the still through a suitable stufling box bearing 55 and is provided at its upper end with a worm-wheel 56, an operative connection being established from a suitable driving motor 57, shown in Figure 1, through a driving chain 58, a sprocket wheel 59, a counter shaft 60 and a worm-gear 61 which meshes with the worm-wheel 56.

The action of the stirrer tends to prevent the aluminum chlorid, the aluminum chlorid sludge formed and any carbon that may be still and keep the aluminum chlorid and the useful catalytic bodies formed --the'refrom in suspension or circulation in the oil.

Recovery stills. The recovery stills 25 and 26 as already pointed out, are arranged one on each side of example, downwardly through the pipe 43' directly into the body of the oil in the main still. In this way practically none of the aluminum chlorid is lost and et the sludge may be drawn 06 at suitable intervals from the bottom of the main still, thus enabling the operation to be continuous as hereinafter explained.

In order to avoid the aluminum chlorid vapors from being condensed as they pass over from the recovery still to the main still, I prefer to utilize a jacket or casing 67 for each of the pipes 39 and 40. Each of these jackets, as clearly shown in Figures 13 and 14, may be made of sheet metal and may be lagged on the outside if desired. Each is suificiently large so that it is spaced from the pipe which it surrounds, and suitable heating means is provided in the space for maintaining the temperature of the vapors. The heater shown for this purpose in Figures 13 and 14, comprises a gas pipe 68 which is provided with a circular burner 69 near the bottom of the vertical part of the protecting sleeve, and a perforated horizontal burner 70 for heating the horizontal part of the protector.

If it is desired to recover the aluminum chlorid in the form of a solid, a suitable condenser will be provided such as the condenser 71 in Figure 2. The aluminum chlorid vapors instead ofpassing upwardly into the pipe 40 may be controlled to pass into the sublimer 71 Where they are condensed in the form of solid anhydrous aluminum chlorid.

If the aluminum chlorid is recovered in this manner it of course may be introduced in the mixing chamber 27 either alone or as a part of the fresh charge which enters the system at this point as more fully explained hereinafter.

Aluminum chlorid mim'ng apparatus.

The aluminum chlorid mixing apparatus which is designated 27 comprises a vertical receptacle or drum which is connected by a pipe 38 to the still 22 as already explained. The pipe 38 is provided with a control valve 72 and the mixing apparatus, as clearly shown in Figures 7, 8 and 9, is provided with a stirrer 73 comprisin 1 a' shaft 74 mounted on a thrust bearing 75 at the bottom of the mixing tank and extending u wardly through a suitable hearing or stu ing box 76 at the top of the tank.

Secured to the shaft within the tank are a plurality of radial stirring blades 77, and the shaft, together with the stirring blades is rotated by means of a motor 78 which drives a pinlon 79, the operative connection being completed by a gear wheel 80 and a countershaft 81 on which is a bevel gear 82 in mesh with a bevel gear 83 at the upper end of the shaft 74.

Furthermore the mixing tank 27 is provided with a gas outlet pipe 84, having a control valve 85, said outlet being coupled to a standpipe 86 in such manner that the connection may be opened and fresh charges of anhydrous aluminum chlorid introduced in powdered form through the standpipe into the mixing tank.

The mixing tank is provided with oil through a pipe 87 having a control valve 88, and oil may be conveniently charged into the main st-ill'by way of pipe 38 through a pipe 89' controlled by a valve 90 or direct to the still by means of pipe 110 controlled into the recovery stills.

by valve 111, the pipes 89 and 110 terminating in a common supply pipe 112 controlled by valve 113 and in communication with the pump 114, as clearly shown in Figure 16. The pump has a valved connection 116 extending to a source of oil supply as the tank 117. The pipe 87 for supplying oil to the mixer 27 is in communication with the pump outlet 112. Thus the oil to be treated may readily be introduced to the mixer and to the still as required.

It frequently happens that in drawing off the sludge materials from the main still into the coking stills 25 and 26 more or less liquid oil suitable for treatment with aluminum chlorid is drawn 011: with the Sludge This oil may'be returned to the still 22 in the form of vapor through the recovery lines.- However, it is often undesirable to do this and it is gene'rally preferable to draw off the liquid oil from the recovery stills caving only the sludge materials to be heated for the recovery of the aluminum chlorid. For this purpose the pump intake line 116 may have a branch connection 118 having the valve 119 and the valved branch lines 120 and 121 connected to the recovery stills 25 and 26 respectively. The oil collected in the recovery stills may thus be withdrawn and returned either to the mixer or the main still for further use.

The mixing tank 27 is preferably heated and is adapted to be. maintained at the desired temperature by means of a steam heating coil 107 which is supplied With steam through a control valve 108, steam being discharged through an outlet valve 109.

Air and water condense-rs.

Suitable air condensers with back trap lines are provided for returning to the still any portions of oil which have not been sufficiently treated. The construction illustrated embodies certain means for controlling the operation in the still, which are not claimed herein per se, but which are well adapted for use in connection with the processes claimed in this application. In the arrangement illustrated a vertical column or vapor tower 91 is provided having a plurality of outlet branches 92, each provided with. a control valve 93 and all terminating in a manifold pipe 94. This pipe connects with a discharge pipe 95 which extends to the water condenser 29.

The oil vapors from the main still pass out through the oil vapor line 37 into a preliminary separating tank or chamber 96 which is connected at the top to a second separator tank 97, both separating tanks and the column 91 of the air condenser being connected to the common back trap line 49. From the separator chamber 97 connection may be established through control valve 98 to the air condenser column 91, or through control valve 99 directly to pipe 95 which is connected to the water-condenser.

By means of the control tower 91 and effective control of the distillation in the still may be easily accomplished without varying the furnace fire, the temperature of the vapors taken from the tower being regulated by the valves 93.

The water condenser comprises a cooling coil 100 from which condensed liquid flows The operation.

In operating the apparatus and continuously practicing my improved process, the main still is filled with a suitable amount of oil to be cracked or treated through either of the charging lines 89 or 110. Oil is also admitted through charging line 88 to the mixing tank or chamber 27. The cap, together with the gas escape line 84, is removed rom the standpipe 86 and a suitable quantity of aluminum chlorid is introduced, into the standpipe in the form of a powder.

The motor 78 is then operated to drive the mixer 73, the blades 77 being thus rotated andthoroughly mixing the aluminum chlorid with the Oil in the mixing tank. The mixture of aluminum chlorid and oil is next allowed to gravitate through the pipe 38 into the main still and while the mixing tank may be located in any suitable position and the material be pumped from the mixing tank to the still, I have found that adirect, open passage through which the material may gravitate, into the still, is the best, as the mixture is very liable to clog a pump and a certain amount of the material is liable to be lost unless the connection is direct and open.

- not exceed150 F. although at times a temperature of as high as 350 F. may be used to advantage especially when using crystalline aluminum chlorid.

When the aluminum chlorid and oil mixture is at the proper temperature and thoroughly mixed the valve 72 is opened and the contents of the mixing chamber permitted to flow directly into the still. The valve 72 is then closed and art additional mixture may be prepared in the mixing tank at any tune.

The main furnace is operated to mamtain .the oil in the still at distilling temperatures. The vapors of the treated or cracked oil, pass out through the vapor line 37 through the trap tanks 96 and 97 which permit any heavy products carried over,'to pass back through the back trap line 49 and out through the valve 98 if it is open, into the column 91 of the air condenser 28. From this column all but the desired final product flows back into the back trap line 49 and the final product vapors pass over through line 95, are condensed in the water condenser coil -100, and finally flow into the drum 30 from which they may be withdrawn as desired.

As the process continues say, for 24 hours, aluminum chlorid in the still becomes more or less exhausted and the main still accumulates considerable sludge containing a mix ture of partially spent aluminum chlorid, and hydrocarbons. This sludge or residue is then drawn 0d through one of the pipes 6566 into the corresponding recovery still. When so drawn ofi the passage is closed, additional aluminum chlorid and oil mixture is introduced from the mixing chamber 27, the supply of oil being periodically replenished throughthe charging line 89.

The second charge of aluminum chlorid and oil from the mixer will not contain as much aluminum chlorid as the first because when heat is applied to the recovery still, aluminum chlorid is driven off therefrom in the form of vapor which is not allowed to condense due to the heating of the passage as already explained and the valve 42, for example, being open the vapors pass directly into the oil in the still. In this way none of the aluminum chlorid is lost in the sludge but is returned and performs its share of the work in connection with the newly introduced charge from the mixer. When all the aluminum chlorid has been driven off from one recovery still that still is shut down, the valve 42 for example, being closed and the coke is removed, the other recovery still being then available so that the process goes on without interruption.

In other words, the recovery stills will be utilized in alternation, one being open for cleaning while the other is in use. Any aluminum chlorid which may be condensed in the T-connection 44 or any carbon 01' sludge materials collecting therein may be scraped off and allowed to fall into the still by operating the scraper 45 which is accomplished by means of the handle 48.

Apparatus of preferred form and a preferred method of carrying out my process have been described for the purpose of showing a way in which this invention may be .used, but the inventive thought on which this application is based, is broader than these illustrative embodimentsthereof, and I therefore intend that only such limitations be imposed as are indicated in the appended claims.

What I claim is:

1. Apparatus for treating hydrocarbons comprising a still, a mixing chamber for aluminum chlorid and oil connected with the still, a pair of recovery stills adapted to receive sludge fromthe main still and con nected to discharge aluminum chlorid vapors into the main still;

2. Apparatus for treating hydrocarbons comprising a still, a mixing chamber for aluminum chlorid and oil connected with the still, a pair of recovery stills adapted to receive sludge from the main still and connected to discharge aluminum chlorid vapors into the main stills being arranged to tion so as to therefrom.

3. Apparatus for treating hydrocarbons comprising a still, a mixing chamber for aluminum chlorid and oil connected with the still, means for stirring the mixture of aluminum chlorid and oil in the mixing chamber, means for agitatingv the oil and aluminum chlorid mixture within the said still, a pair of recovery stills adapted to restill, said recovery be used in alternapermit the removal of coke izs ceive sludge from the main still and connected to discharge aluminum chlorid vapors into the main still.

4. Apparatus for treating hydrocarbons comprising a still adapted to contain oil and aluminum chlorid, a recovery still adapted to receive sludge from the main still, a connection for returning aluminum chlorid va- I pors from the recovery still to the main still and means for heating the vapor connection to prevent condensing of the aluminum chlorid therein.

5. Apparatus for treating hydrocarbons with aluminum chlorid comprising a still, a mixing chamber for aluminum chlorid and oil superposed directly above said still, means for admitting oil and aluminum chlorid to said mixing chamber, a direct vertical connection extending from the bottom of the mixing chamber to the still, a supplemental recovery still adapted to receive residue from the main still and means for returning aluminum chlorid vapors from the recovery still to the main still.

6 Apparatus 'for treating hydrocarbonscomprising a main still, a mixing chamber for aluminum chlorid and oil connected to" introducing oil to the still, means for periodically admitting aluminum chlorid to.the still, means for withdrawing from the still residue containing aluminum chlorid, means for coking said residue without admitting extraneous gas thereto and means for cor.- ducting gases evolved in the coking back to the still.

8. The process of converting higher boiling oils into lower boiling oils which comauxiliary heating chamber without exposure to the atmosphere, driving oil the aluminum chlorid from the sludge by coking the latter, and passing the vapors of the aluminum chlorid into the same body of oil from which the sludge was withdrawn.

9. The process for converting high boiling oils into'lower boiling oils which comprises agitating and heating a mixture of oil and aluminumchlorid until the activity of the aluminum chlorid becomes so reduced that the distillation has proceeded to the extert desired, withdrawing a portion of the heavier oily sludge containing partially spent aluminum chlorid, passing said sludge without contact with the atmosphere to an auxiliary heating chamber, coking the sludge in said chamber, and conducting the aluminum chlorid vapors thus generated into the original mixture being treated.

10. The process of converting higher boiling oils into lower boiling oils in the presence of aluminum chlorid and continuously recovering and re-using the aluminum chlorid which comprises heating a mixture of oil and aluminum chlorid to produce vapors pors of aluminum chlorid directly to a mixv ture of oil and aluminum chlorid undergoing conversion.

In witness whereof'I have hereunto set my hand this 6th day of February, 1920.

GEORGE D. WHITE.

GER'iiiiGA'iE or connection,

Patent Nob 1,726,281). Y (Granted August 27, me, te

' enonen n. wetter It is hereby certiiiedthat error appears in the printed specification of the above numbered patent requiring correction as foiiows: Page i, tine 34, hetore the period insert the words with parts broken away"; tine 62, eiter the Word "view" insert "taken on the line 10-10 of Fignrell"; time 89, strike eat the numerai "28" and insert instead "or dephiegmater 91''; line 90, for "eoiiem ing" read "distillate"; same line, strike out the word "from"; iines 9i and 92, strike out "which the treated or eraeked oil! is withdrawn"; page 2, line I 117, for "snblimer" read "condenser"; and that the said Letters Patent shoiiid be read with these corrections therein that the same may eonierm to the reeord of .the casein the Patent Office.

'Signed and'seaied this 15th day ot @ctoher, A. D, 1929.

. M. J. Moore, (Seal) 4 Aeting Sommiwioner ot Petente. 

